EP0395360B1 - Verfahren zur Herstellung von sec.-Butylbenzol - Google Patents

Verfahren zur Herstellung von sec.-Butylbenzol Download PDF

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Publication number
EP0395360B1
EP0395360B1 EP90304403A EP90304403A EP0395360B1 EP 0395360 B1 EP0395360 B1 EP 0395360B1 EP 90304403 A EP90304403 A EP 90304403A EP 90304403 A EP90304403 A EP 90304403A EP 0395360 B1 EP0395360 B1 EP 0395360B1
Authority
EP
European Patent Office
Prior art keywords
butylbenzene
sec
benzene
butene
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90304403A
Other languages
English (en)
French (fr)
Other versions
EP0395360A1 (de
Inventor
Mitsuhisa Tamura
Kazuhiro Yamauchi
Yasuhiko Higashio
Kazuteru Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication date
Priority claimed from JP2048849A external-priority patent/JP2797609B2/ja
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of EP0395360A1 publication Critical patent/EP0395360A1/de
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Publication of EP0395360B1 publication Critical patent/EP0395360B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/70—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C07C2527/10—Chlorides
    • C07C2527/11—Hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

Definitions

  • the present invention relates to a process for production of sec-butylbenzene from benzene and n -butene.
  • sec -Butylbenzene produced by the present invention is particularly useful for use as a starting material for production of phenol and methyl ethyl ketone through the respective steps of air oxidation and decomposition.
  • Phenol can be used as a starting material for production of synthetic resins and antioxidants, and methyl ethyl ketone can be used as a solvent or for dewaxing of lubricating oils.
  • JP-A-50-137933 discloses a method in which a liquid aluminum chloride complex catalyst is used in such an amount that the amount of aluminum chloride is from 0.05 to 0.25% by weight of the reaction mixture.
  • the product is a mixture mainly containing sec -butylbenzene (SBB), isobutylbenzene (IBB), dibutylbenzenes (DSBB), and tributylbenzenes (TSBB).
  • SBB sec -butylbenzene
  • IBB isobutylbenzene
  • DSBB dibutylbenzenes
  • TSBB tributylbenzenes
  • dibutylbenzenes and tributylbenzenes are each separated from the reaction mixture and then transalkylated into sec -butylbenzene. This reaction can be illustrated as follows:
  • Boiling points of isobutylbenzene and sec -butylbenzene are 172.8°C and 173.5°C, respectively, and are close to each other. Thus it is difficult to separate these two compounds from each other by distillation. Isobutylbenzene formed as a by-product in the reaction is sent as such to an air oxidation step along with sec-butylbenzene. It is known, however, that if sec-butylbenzene contains isobutylbenzene, the rate of reaction in the air oxidation step is markedly decreased (see JP-A-48-80524).
  • the rate of oxidation of sec-butylbenzene decreases to about 91% of that when the sec-butylbenzene does not contain isobutylbenzene at all.
  • the rate of oxidation decreases to about 86%; when the isobutylbenzene content is 2% by weight, the rate of oxidation decreases to about 84%; and when the isobutylbenzene content is 3.5% by weight, the rate of oxidation decreases to as much as about 82%.
  • the present invention is intended to overcome the above problems, and an object of the present invention is, therefore, to provide a process for production of sec -butylbenzene in a high yield while maintaining the amount of isobutylbenzene formed as a by-product at a low level.
  • the present invention relates to a process for producing sec-butylbenzene from benzene and n-butene in the presence of a liquid aluminum chloride complex catalyst as defined below, wherein the amount of aluminum chloride used as a component of the complex catalyst is from 0.3 to 5% by weight of the benzene to be used in the reaction, the reaction temperature is from 20 to 90°C, and the amount of isobutylbenzene formed as a by-product is controlled to not more than 1% by weight of sec-butylbenzene formed.
  • the liquid aluminum chloride complex catalyst (hereinafter referred to as a "complex catalyst") to be used in the present invention refers to a homogeneous complex catalyst, comprising aluminum chloride, hydrogen chloride and an aromatic hydrocarbon.
  • aromatic hydrocarbon sec -butylbenzene, ethylbenzene, di- sec -butylbenzene, and tri-sec-butylbenzene can be used alone or in admixture of two or more thereof. Of these, sec-butylbenzene is most suitable.
  • hydrogen chloride and aromatic hydrocarbon are used in amounts of 1 mole and 2 to 10 mole, respectively, per mole of aluminum chloride.
  • the complex catalyst In preparation of the complex catalyst, it suffices that the above components are mixed and stirred into a homogeneous solution. This is attained by stirring at room temperature for from about 20 minutes to 3 hours.
  • the complex catalyst thus prepared can be used as such in the reaction of benzene and n-butene.
  • the complex catalyst after being used in the reaction, can be separated from the reaction mixture and reused in the reaction.
  • n -Butene to be used in the present invention can be 1-butene, cis -2-butene or trans -2-butene.
  • mixtures of the above compounds can be used, and mixtures of n-butene and compounds inert to the reaction, such as butane, can be used.
  • the amount of n -butene used is preferably from 0.1 to 1.2 mole, more preferably from 0.4 to 1.1 mole, per mole of benzene. If the amount of n -butene used is too small, the volume efficiency of the reaction is decreased, and the cost for separation of sec -butylbenzene from the reaction mixture is increased. On the other hand, if the amount of n -butene used is too large, by-production of alkylbenzenes having two or more butyl groups undesirably increases.
  • the amount of aluminum chloride in the complex catalyst is from 0.3 to 5% by weight, more preferably from 0.3 to 1% by weight, based on the amount of benzene used in the reaction. If the amount of the complex catalyst used is less than the above specified range, the reaction must be carried out at elevated temperatures in order to proceed the reaction sufficiently. In this case, formation of an undesired by-product, isobutylbenzene increases. On the other hand, if the amount of the complex catalyst used is in excess of the above specified range, the catalyst cost is undesirably increased. Also, in this case, formation of undesired by-product, isobutylbenzene is increased.
  • the reaction temperature is from 20 to 90°C, preferably from 20 to 70°C. In the case that the reaction temperature is higher than this range, formation of isobutylbenzene increases. On the other hand, in the case that the reaction temperature is lower than the above-specified range, the reaction for formation of sec-butylbenzene does not thoroughly proceed. In this case, if in order to make the reaction thoroughly proceed, the amount of the catalyst used is increased, formation of isobutylbenzene undesirably increases.
  • the most significant advantages of the present invention are in that by setting up an optimum combination of a relatively low reaction temperature with a relatively high amount of the catalyst as compared with those in the conventional techniques, not only formation of undesirable by-product isobutylbenzene is inhibited, but the desired reaction can proceed thoroughly to a sufficient extent.
  • the reaction pressure is not critical.
  • the amount of isobutylbenzene formed as a by-product in the reaction mixture obtained by the present invention can be maintained at not more than 1%, preferably not more than 0.8%, by weight of sec -butylbenzene formed.
  • the significance of maintaining the ratio of isobutylbenzene to sec -butylbenzene formed at a low level is as described hereinbefore.
  • the present reaction can be carried out batchwise or continuously.
  • Separation and recovery of sec -butylbenzene from the reaction mixture obtained in the reaction of benzene and n -butene in the present invention can be carried out by the usual techniques.
  • the reaction mixture is washed with water to inactivate the complex catalyst.
  • the residue is further washed with an aqueous sodium hydroxide solution to remove the complex catalyst completely, and then separated into an oil layer and an aqueous layer.
  • the oil layer thus obtained is distilled into a fraction mainly containing sec-butylbenzene, a fraction mainly containing dibutylbenzenes and tributylbenzenes, a fraction mainly containing heavy materials, and a fraction mainly containing unreacted benzene.
  • the fraction containing dibutylbenzenes and tributylbenzenes is recycled to the aforementioned transalkylation step where they are converted into sec -butylbenzene.
  • the unreacted benzene is returned to the step where sec-butylbenzene is produced from benzene and n -butene.
  • the fraction mainly containing dibutylbenzenes and tributylbenzenes is returned to the reaction zone of benzene and n -butene.
  • the complex catalyst used in the reaction is, after completion of the reaction, separated and recovered from the reaction mixture by the liquid-separating operation, and the complex catalyst thus separated is recycled to the reaction zone of benzene and n -butene.
  • sec -Butylbenzene obtained by the process of the present invention can be suitably used as a starting material for production of phenol.
  • a method of production of phenol from sec -butylbenzene is described in, for example, JP-A-48-80524. That is, sec -butylbenzene is oxidized into sec -butylbenzene hydroperoxide at from about 75 to 140°C. Then the sec -butylbenzene hydroperoxide is concentrated and decomposed with an acid catalyst to produce phenol and methyl ethyl ketone.
  • reaction mixture was cooled to room temperature, and the reaction mixture was taken out of the flask, washed with 30 g of a 30 wt% aqueous sodium hydroxide solution to inactivate the catalyst, and then liquid-separated. Then, the reaction mixture was analyzed by gas chromatography under the conditions shown below to determine the composition. The results are shown in Table 2.
  • Example 2 The procedures of Example 1 were repeated with the exception that the amount of the complex catalyst and the reaction temperature were changed as shown in Table 2. The results are shown in Table 2.
  • Example 2 The procedures of Example 1 were repeated with the exception that the amount of the complex catalyst and the reaction temperature were changed as shown in Table 2 and that a mixed butene shown in Table 1 was used in place of 1-butene. The results are shown in Table 2.
  • the total amount of 1-butene, cis -2-butene and trans -2-butene used was 1 mole.
  • Example 2 The procedures of Example 1 were repeated with the exception that the amount of the complex catalyst and the reaction temperature were changed as shown in Table 2. The results are shown in Table 2.
  • reaction mixture was cooled to room temperature, taken out of the flask, washed with 30 g of a 30 wt% aqueous sodium hydroxide solution to inactivate the catalyst, and then separated.
  • the composition of the reaction mixture was analyzed by gas chromatography. The results are shown in Table 2.
  • Comparative Example 1 in which the amount of the complex catalyst was less than the range specified in the present invention, the reaction proceeded insufficiently (benzene conversion was low). Also, in Comparative Example 2 in which the amount of the complex catalyst was more than the range specified in the present invention, the undesired by-product, isobutylbenzene was markedly formed.

Claims (6)

  1. Verfahren zur Herstellung von sek-.Butylbenzol aus Benzol und n-Buten in Gegenwart eines homogenen flüssigen Aluminiumchloridkomplexkatalysators, umfassend Aluminiumchlorid, Chlorwasserstoff und einen aromatischen Kohlenwasserstoff, wobei der Katalysator durch Einleiten von Chlorwasserstoffgas in ein Gemisch aus Aluminiumchlorid und dem aromatischen Kohlenwasserstoff erhalten wird, wobei das Verhältnis von Aluminiumchlorid zum aromatischen Kohlenwasserstoff 2 bis 10 Mol des aromatischen Kohlenwasserstoffes pro Mol Aluminiumchlorid beträgt und der aromatische Kohlenwasserstoff sek.-Butylbenzol, Ethylbenzol, Di-sek-butylbenzol, Tri-sek-butylbenzol oder ein Gemisch davon ist, in dem die Menge des als Bestandteil des Komplexkatalysators verwendeten Aluminiumchlorids 0,3 bis 5 Gew.-% des verwendeten Benzols beträgt, die Umsetzungstemperatur 20 bis 90°C beträgt, und die Menge des als Nebenprodukt gebildeten Isobutylbenzols so ist, daß das Gewichtsverhältnis von Isobutylbenzol zum gebildeten sek-Butylbenzol nicht mehr als 0,01:1 ist.
  2. Verfahren nach Anspruch 1, in dem die Menge des als Bestandteil des Komplexkatalysators verwendeten Aluminiumchlorids 0,3 bis 1 Gew.-% des verwendeten Benzols beträgt.
  3. Verfahren nach Anspruch 1 oder 2, in dem das Molverhältnis des umzusetzenden Benzols zu n-Buten 1:1,0 bis 1:1,2 beträgt.
  4. Verfahren nach Anspruch 3, in dem das Molverhältnis des umzusetzenden Benzols zu n-Buten 1:0,4 bis 1:1,1 beträgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, in dem das durch Umsetzung von Benzol und n-Buten erhaltene Reaktionsgemisch in eine hauptsächlich Benzol enthaltende Fraktion, eine hauptsächlich sek-.Butylbenzol enthaltende Fraktion, eine hauptsächlich Dibutylbenzole und Tributylbenzole enthaltende Fraktion und eine hauptsächlich schwere Substanzen enthaltende Fraktion aufgetrennt wird, und die hauptsächlich Benzol enthaltende Fraktion und die hauptsächlich Dibutylbenzole und Tributylbenzole enthaltende Fraktion wieder in die Reaktionszone des im Anspruch 1 definierten Verfahrens zurückgeführt werden.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in dem die Umsetzungstemperatur 20 bis 70°C beträgt.
EP90304403A 1989-04-25 1990-04-24 Verfahren zur Herstellung von sec.-Butylbenzol Expired - Lifetime EP0395360B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10665789 1989-04-25
JP106657/89 1989-04-25
JP48849/89 1990-02-27
JP2048849A JP2797609B2 (ja) 1989-04-25 1990-02-27 ｓｅｃ―ブチルベンゼンの製造方法

Publications (2)

Publication Number Publication Date
EP0395360A1 EP0395360A1 (de) 1990-10-31
EP0395360B1 true EP0395360B1 (de) 1994-03-16

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ID=26389183

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90304403A Expired - Lifetime EP0395360B1 (de) 1989-04-25 1990-04-24 Verfahren zur Herstellung von sec.-Butylbenzol

Country Status (4)

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US (1) US5059736A (de)
EP (1) EP0395360B1 (de)
CA (1) CA2015191A1 (de)
DE (1) DE69007323T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19844085C1 (de) * 1998-09-25 2000-03-16 Siemens Ag Verfahren zum Steuern einer Brennkraftmaschine abhängig von einem Abgasdruck

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2884820B2 (ja) * 1990-09-10 1999-04-19 住友化学工業株式会社 ｓｅｃ−ブチルベンゼンの製造法
US7671248B2 (en) * 2004-08-13 2010-03-02 Exxonmobil Chemical Patents Inc. Process for producing sec-butyl benzene
TWI376361B (en) * 2004-08-13 2012-11-11 Exxonmobil Chem Patents Inc Process for producing phenol and methyl ethyl ketone
TW200744986A (en) * 2006-02-14 2007-12-16 Exxonmobil Chemical Patents Inc Process for producing phenol and methyl ethyl ketone
US7834218B2 (en) * 2006-02-14 2010-11-16 Exxonmobil Chemical Patents Inc. Process for producing phenol and methyl ethyl ketone
TW200744985A (en) * 2006-02-14 2007-12-16 Exxonmobil Chemical Patents Inc Process for producing sec-butylbenzene
DE602008005752D1 (de) * 2007-08-22 2011-05-05 Exxonmobil Chem Patents Inc Verfahren zur herstellung von sec.-butylbenzol
EP2098498A1 (de) 2008-03-04 2009-09-09 ExxonMobil Chemical Patents Inc. Selektive Oligomerisierung von Isobuten
WO2009082464A1 (en) * 2007-12-21 2009-07-02 Exxonmobil Research And Engineering Company Process for producing phenol and methyl ethyl ketone
KR20110016964A (ko) * 2008-08-26 2011-02-18 엑손모빌 케미칼 패턴츠 인코포레이티드 알킬벤젠 하이드로퍼옥사이드의 제조방법
WO2010042268A1 (en) * 2008-10-10 2010-04-15 Exxonmobil Chemical Patents Inc. Process for producing sec-butylbenzene
WO2010042269A1 (en) * 2008-10-10 2010-04-15 Exxonmobil Chemical Patents Inc. Process for producing phenol and methyl ethyl ketone
KR20110086162A (ko) 2008-12-15 2011-07-27 엑손모빌 케미칼 패턴츠 인코포레이티드 알킬방향족 화합물의 산화

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Also Published As

Publication number Publication date
EP0395360A1 (de) 1990-10-31
US5059736A (en) 1991-10-22
DE69007323T2 (de) 1994-07-14
DE69007323D1 (de) 1994-04-21
CA2015191A1 (en) 1990-10-25

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